Starch modification



Patented May I I s'rnncn MODIFICATION Joseph K."n.se1bei-1ich, Medfield, Mass.

No Drawing. Application November 4. 1940,

Serial No. 364,241

.2 Claims. (!.127-33) Y The present invention'relates to the manufacture of starch products, and has for its principal object the modification ofstarch to render it suitable for use in the manufacture of products of great transparency.

I Another object of the invention is the production of starch products of considerable strength and more especially a film of considerable strength and great transparency. This application is a continuation in part of my pending application Serial No. 276,661, filed May 31, 1929.

Starch is an amorphous, hygroscopic, velvety substance consisting of fine granules or grains which have a more or less concentric structure. These starch granules are composed of an outer wall and an inner'core or sol, the wall consisting of amylopectin or alpha amylose and the core.

consisting of beta amylose. Chemically, starch is regarded as a polyglucosidic combination of glucose'units, I I I It has been known to produce thin, clearstarch solutions and to, cast such solutions'into opaque or non-transparent films byiorming a suspension pf starch in water and subsequently oxidizing I such suspension by-meansof oxidizing agents,

stantial oxidation or disintegration takes place, the swollen material is washed to remove the swelling agent. Preferably, during the treatment, the suspension is maintained slightly alkaline. Good results have been obtained where the pH value is between 7 and 8.5. Such pretreatment increases the swelling characteristics of the outer wall of the starch granule rendering it more elastic and transparent thereby making the dividing line between the wall and inner portion less definite and'more diificult to observe microscopically.- Since the swelling properties of the granules are, increased, the long chains, of glucose units are not subsequently split into smaller units and, hence, the important physical and chemical properties of the original starch are not materially altered.

Any ,non-acidic substance, which in aqueous solution, is known to be capable of swelling starch granules may be:used in: the pretreatment of starch in accordance with the invention. Among such substances are oxidizing agents, such as sodium or calcium hypochlorite, hydrogen peroxsuch as 'caIQium-hypochIorite. The oxidation processes of starch as heretofore carried out re- I sulted in at least partial decomposition or de-,- Z

polymerization of the long, complicated chains of glucose units into shorterand less complicated .glucose units, and the destruction of the walls of the granules.

I have determined that a starch film produced by such process is relatively weak and that this weakness is due ain1y to the fact that the original structure o the' tarch granules has been substantially or completely destroyed. I have discovered that better starch films can be produced if the breaking up or decomposing of the starch granules, particularly the walls thereof, can be prevented.

In its broad aspect, the invention contemplates a pretreatment of starch to render the outer wall of the starchgranules more elastic and increase their swelling, properties. This is accomplishedby subjecting an aqueous suspension of the starch to the action of an extremely weak solution of any suitable "swelling agent at a temperature below the temperature at which gelatinization oi the starch. takes place and fora period time such that maximum swelling is obtained without substantial oxidation or, disintegration. The concentration of. swelling agent and temperature used ar interdependent, that is, if one is increased, the other must be lowered. Before subide, sodium perborate and the like, and nonoxidizing substances, such as potassium sulfocyanate, urea, thio-urea and sodium bromide. Since such substances are well known as starch swelling agents and since they do not fall in any recognizedchemical class they will be referred to as swelling agents."

The invention i applicable to starch ,from any source but potato starch is preferred because of its low cost. It is desirable to use the raw potato starch as obtained by grinding potatoes with a water content of'fromlO to 15% by weight because there would be no advantage in drying the starch and then adding water to it. Furthermore, starch may change chemically when heated or dried and any chemical change is undesirable.

Starch pretreated in accordance with the invention provides an excellent base material for the manufacture of various starch products either by molding or casting, such as films, sheets,

' threads, filaments, plastics and the like. It may also be used'in th manufacture of plastics by a commercial must be .carried stirring at room temperature C.).

' templates the production of a transparent cast starch film. Thus, in accordance with this aspect of the invention, an aqueous dispersion of below that of the gelatinization temperature and then suddenly brought to a temperature above that of the gelatinization temperature. During heating the dispersion is slowly stirred. After complete gelatizination, heating is continued more strongly until the milky gelatinous mass starch pretreatedas previously described is gelatinized by heating and the heating is continued until the gel tinous liquid mass becomes thin and clear as its temperature approaches the boiling point. The solution: may be thinned by adding water orlike aqueous liquid orthickened by evaporation and then can upon a heated rotatable drum or 4 a film. It is'desirable, to add an agent to prevent the film" becoming brittle. Plasticizers may be used for this purpose, but a hygroscopic agent,

' either organic or inorganic, is preferred. Cal

cium and magnesium chlorides,- calcium and so- I fibrous material.

. it'is to be used as a base for filaments, or thickerred by evaporation if it is to be used for casting travelling metal belt to form dium phosphates,,-'beta ethoxy 'glycolate,'; beta ethoxy lactate, beta ethoxy maleate, menace: tine and'tetraethylene and tetramethylene glycols are suitable for this purpose.

The following-is anillustrative example of the practice of the invention, first, in pretreating the starch. followedby the use ofsuch pretreated starch in the manufacture of a cast transparent Using potato starch'which has a gelatiniza- 'tion temperature of about 66 0., a suspension is formed by putting 500 grams of normal potato starch with a water content weight in a container to'gether'with 500 ccm. of

sodium hypochlorite solution having a chlorine content of about 2 grams per liter which is appreciably less than 1% by weight of the mixture.

gelatinization temperature of the starch.v The suspension is maintained at a pH valueof about 7.2 by neutralizing it, if necessary, with hydrochloric or acetic, acid. With the aforementioned suspension containing about .1% by weight of chlorine, good results have been obtained by At higher temperature the suspension must be more diluted with respect to the chlorine content in order to obtain similar results. After the stirring is brought to an end, the suspension is filtered and washed with water until it is free from hypochlorite.

135 grams of wet starch, pretreated as described above and containing about by weight of water, are placed in a container and 300 com. of cold water are added, thus forming a 25% starch suspension. stirreduntil uniform dispersion is attained to prevent the subs uent formation of lumps. Then, the suspengc m is heated, preferably by placing the container in a boiling water or steam bath, to a temperature somewhat below thatofr the gelatinization temperature] Good results of 10 to 15% by becomes thinand glass clear as its temperature rises to Just below thejboiling point.

At this point the product is a greatly swollen transparent starch gel of a viscosity about equal to that oiglycerin or paraifin oil. This greatly swollen transparent starch solution may be used as a sizing substance for textile, paper or like The solution may be thinned by adding water or like aqueous liquid in case hen the solution is to be used for casting films it is desirable to add to the hot solution ahygroscopic agent, such as calcium chloride, to prevent the cast film from becoming brittle. Good results have been obtained by the addition of from 5 to 10% calcium chloride based upon the weight of the solution. The clear viscous liquid is then run upon a heated rotating drum. The temperature of the drum may be varied between 60 to about 120 C. to permit control of the film thickness. The thickness also may be controlled by varying the speed of rotation of the drum or viscosity of the solution. The" so1u- :tion poured upon the drum dries quickly and the dried film may be removed after a partial revolution of the drum. The film thus produced may be coated in a known manner to render it moisture proof.

The'film issmooth, highly transparent, flexible and of a strength comparable with similar films The starch suspension is slowly stirred for one hour. The slow stirring process out at temperatures helowythe made from cellulose hydrate products. As compared with films made from cellulose and like products, the starch film has the advantage of lower manufacturing cost and greater uniformity. The lower manufacturing cost is due to the relatively low price of raw starch and to the fact that there is no waste in the manufacturing process, defective film may be recast. The cast-- ingsolution may be used with relatively high starch concentration. In the above example,'for instance, the starch content is about 25%, but even higher concentration of starch solution may be readily cast into film and like products in contrast to solutions made from cellulose hydrate which can be cast only in low concentration and therefore require more heat for drying. The great uniformity of starch products is due to the uniformity of the raw material. Starch,

whether potato, corn or other starch, is much more uniform than, for instance, cellulose mate- 1 rial. The 'most remarkable characteristic of This suspension. is

starch products made according to my invention,

aside from their great transparency, is their considerabletensile strength. This strength, as alreadyindicated, is due to the fact that the starch have been obtained in the case of'potato'starch by heating the suspensiontoabout 50 C. while slowly'stirring it. Thereupon sudden" heating is eflected by the addition of 300' cm. of boiling water to the above suspension in order toeflect in my products has-not been oxidized; the original starch .unitsthereforehave retained all their chemical and most 'of thei physical characteristics. The relatively large vesicles are still present and adhere to each other somewhat like the bricks of a wall. If it is desired to dye such starch products, a dyestuif may be added to the starch solution before casting or the product may be dyed by. dipping or spraying after the product is completed-.1, Certain ingredients, pigments or fillers,- forexample, mica, titanium dioxide, in-

somewhat 7s soluble sine, aluminum powder, lead salts, Organic dyers and lakes may be added to the starch solu-v tion before casting. to produce various desirable effects in the finished product.

I claim:

1. In the manufacture of starch products, the steps comprising treating raw starch in suspension in an aqueous solution of sodium hypochiorite with a chlorine content of 0.1 of one percent or less by weight of the suspension at a temperature below the gelatinization temperature of the starch for a period of time such as to obtain maximum swelling of the starch vesicles without substantial oxidation or disintegration thereof, maintaining the pH value of the suspension between 7 and 8.5 during said treatment, washing the thus treated starch, and thereafter heating a suspension of the thus treated starch to a temperature ature of about 15 above its gelatinization temperature to form a glass clear liquid.

2. In the manufacture of starch products, the

sion between 7 and 8.5 during said treatment,

washing the thus treated starch, and thereafter heating a suspension of the thus treated starch to a temperature above its gelatinization temper- ;ature to form a glass clear liquid.

JOSEPH H. SEIBERLICH. 

